KR101083701B1 - Reversible Solid Oxide Fuel Cell Stack and Method for Preparing Same - Google Patents

Abstract

1) a first component comprising at least one metal containing layer (1) having a bonded electrolyte and a sealing layer, wherein said at least one porous metal containing layer (1) receives an electrode; And 2) a second component comprising at least one metal containing layer (1) having a bonded interconnect and a sealing layer, wherein said at least one porous metal containing layer (1) receives an electrode; A single stack of reversible SOFCs is provided. Also provided is a method for fabricating a reversible solid oxide fuel cell stack. The solid oxide fuel cell stack manufactured as described above has improved mechanical stability and high electrical performance, and the process for manufacturing the solid oxide fuel cell stack has a cost saving effect.

Description

Reversible Solid Oxide Fuel Cell Stack and Method for Preparing Same

The present invention relates to a reversible solid oxide fuel cell stack and a method of manufacturing the same.

Solid oxide fuel cells (SOFCs) are well known in the art and exhibit various structures. Common forms include a flat plate design and a tubular design in which an electrolyte layer is sandwiched between two electrodes. During operation, always at a temperature of 500 ° C. to 1100 ° C., one electrode is in contact with oxygen or air and the other is in contact with fuel gas.

High conductivity, a wide range of electrochemically active regions at the electrode / electrolyte interface, chemical and physical stability to a wide range of fuel gases, and structural changes are often accompanied by deterioration of electrical action and therefore minimal microstructural changes during operating time Various properties such as are required for the SOFC.

Under normal operating conditions, a single cell yields less than 1 V. In order to yield higher voltages and power from the SOFC, it is necessary to form a stack with several cells.

The most common manufacturing method for SOFC planar stacks involves manufacturing single cells. These cells form a stack with interconnects, current collectors, contact layers and seals. After combination, these stacks are integrated / sealed by heat treatment while applying a vertical load to secure the seal as well as the electrical contact between the components. During operation, the mechanical / electrical contact of the stack is made stable by applying continuous vertical loads (eg using yokes).

The cells are most commonly manufactured using wet powder processing, which includes tape-casting of a support component (typically an electrolyte or an anode). The cell support component is generally prepared by tape casting of a powder suspension and the active layers (cathodes, electrolytes and anodes) are continuously spray sprayed, with an intermediate sintering step for the other layers. Or by screen printing.

SOFCs are optionally prepared by, for example, electrochemical vapor deposition (CVD) or plasma spraying. However, the process is very expensive and a need for low manufacturing costs is required.

As a result, when manufacturing flat SOFCs, the emphasis is placed on minimizing sealing and sealing surfaces because the sealing requirements are very stringent. Suitable high temperature sealants that may be used include cement, glass and glass-ceramic sealants. Sealants selected for planar SOFCs must have sufficient stability in oxidation and reducing environments, chemical compatibility with cell-stack components, and suitable sealing and insulating properties. Examples of glass and glass-ceramic sealants developed for flat SOFCs include modified borosilicate glass and aluminum silicate glass.

US-A-200400115503 discloses a porous electrically conductive support layer; Prefabricated electrochemical device layers; And a bonding layer between the support layer and the electrochemical device layer. Also preparing a porous electrically conductive support layer; Preparing a prefabricated electrochemical device layer; And bonding the support layer and the electrochemical device together with a bonding layer.

US-A-6,458,170 relates to a method for manufacturing a bilayer structure consisting of a porous substrate having a bonded high density film, which method comprises forming a uniform porous substrate layer and curing it to a predetermined green density. Spraying a uniform suspension of film material in a volatile carrier over the surface of the substrate using an aerosol spray to form a thin green film layer of predetermined thickness; Evaporating the carrier, and firing a double layer formed by the green film layer and the substrate layer to sinter the thin green film layer and the substrate, wherein the substrate is formed of the fired green film and substrate layer. The overall shrinkage rate has a predetermined green density selected such that the film shrinkage rate can be equal to or smaller than the shrinkage rate of the fired substrate.

Y. Matus et al., “Metal-supported solid oxide fuel cell membranes for rapid thermal cycling,” Solid State Ionics, 176 (2005), 443-449, relate to SOFC membranes, the zirconia-based The electrolyte foil film is supported by the porous material metallic / ceramic current collector and provides fast thermal cycling between 200 ° C and 800 ° C.

US-A-6,843,960 discloses a method for producing a metal or metal alloy plate, which method comprises adding a solvent, a dispersant, a plasticizer and an organic binder to the powder to form a powder of a predetermined composition to form a slip. step; Forming a layer on the substrate with the slip; Forming an additional layer immediately above said layer and forming an additional plurality of layers immediately above said layer to produce a multilayer graded stack in a predetermined order; Exhausting the binder by heating the multilayer classification stack to a predetermined temperature; And sintering the layer at a set temperature in a reduced state for a predetermined period of time.

US-A-20030232230 relates to a SOFC repeat unit comprising a multilayer laminate, the multilayer laminate comprising: a metallic air flow field; A metal interconnect disposed in the metal air flow field; A metal fuel flow field disposed in the metal interconnect; An anode disposed in the metal fuel flow field, and an oxidizing electrolyte disposed on the anode. The manufactured sintering repeat unit forms a stack to form SOFC, and the stack is sealed after sintering.

WO 03/075382 comprises repeatedly laminated anode, electrolyte, cathode and interconnect layers, the interconnect layer comprising a plurality of gasket elements separated from the interconnect, electrolyte, and The gasket component discloses a solid oxide fuel cell of the type characterized in that it has an integral manifold for fuel, oxidant inlet and exhaust stream.

GB-A-2400723 discloses a medium temperature solid oxide fuel cell, which is a ferritic stainless steel substrate comprising a fine porous support and a nonporous frame covering the porous support, the nonporous And a first electrode layer disposed in the frame and supported internally by the fine porous support, an electrolyte layer disposed on the first electrode layer, and a second electrode layer disposed on the electrolyte layer.

US-A-20020048699 relates to SOFC, comprising: a ferritic stainless steel substrate comprising a porous portion and a nonporous portion bonded to the porous portion; A ferritic stainless steel bipolar plate disposed under one surface of the porous portion of the substrate and sealed in contact with the nonporous portion of the substrate near the porosity; A first electrode layer disposed over the other surface of the porous portion of the substrate; An electrolyte layer disposed on the first electrode layer; And a second electrode layer disposed on the electrolyte layer.

WO 02/09116 comprises repeatedly stacked anode, electrolyte, cathode and interconnect layers, the interconnect layer comprising a plurality of gasket components separated from the interconnect, electrolyte and bonded to the anode and cathode components. A solid oxide fuel cell of the type is disclosed. The interconnect, electrolyte and gasket components provide an integral manifold for fuel, oxidant inlet and exhaust flow streams.

US-A-6,248,468 discloses a method for manufacturing a fuel cell, which method provides an air electrode equipped with a pre-sintered nickel-zirconia fuel electrode and a ceramic electrolyte disposed between the electrodes. It includes a step. The fuel electrode is sintered to produce an active solid oxide fuel cell.

US-A-5,908,713 relates to a method of forming a fuel electrode on an electrolyte of an SOFC by a sintering process, the method comprising providing an electrolyte in the form of a slurry and then drying to prepare a lower layer. An upper layer is then formed in the lower layer and dried. Thereafter, the dried lower and upper layers are sintered to form a fuel electrode.

However, the structures and fabrication methods of SOFC stacks known to date have several disadvantages.

1. The ideal single plate stack cannot be manufactured because the stack's mechanical integrity requires semi-permanent mechanical loads to maintain sealed and electrical contact during operation.

2. These manufacturing methods include complex and numerous sintering steps or expensive chemical or physical deposition techniques.

3. There are two disadvantages when sintering electrodes:

a. Due to the required sintering temperature, interface reactions that limit operation are often observed between the electrodes and the electrolyte and / or interconnects;

b. During sintering, it is impossible to maintain sufficient fine microstructure inside the electrode and inside the electrode / electrolyte due to excessive granulation.

In view of the shortcomings of the processes so far known as prior art, an object of the present invention is to provide an SOFC monolithic stack, and a solid oxide fuel cell stack with improved mechanical stability and high electrical performance while having cost savings. It is for providing a manufacturing method of. The stack thus prepared is for operation at a temperature in the range of 450-850 ° C. The stack can operate reversibly when functioning as an electrolyser (Solid Oxide Electrolyzer Cell, SOEC), which may have a higher operating temperature. The stack can also operate under pressurized conditions, such as the conditional characteristics of a gas turbine plant.

This object can be achieved by a reversible SOFC single stack comprising the following components:

1) a first component comprising at least one porous metal containing layer (1) having an electrolyte layer (4) bonded to the sealing layer, wherein the at least one metal containing layer contains an electrode;

2) a second component comprising at least one porous metal containing layer 1 having an interconnect layer 5 bonded to the sealing layer, wherein the at least one metal containing layer contains an electrode.

The object can be achieved by a method for producing a single stack of reversible solid oxide fuel cells, the method comprising the following steps:

Preparing a first component comprising at least one porous metal containing layer (1);

Forming an electrolyte layer (4) on at least one porous metal containing layer (1) of said first component;

Preparing a second component comprising at least one porous metal containing layer (1);

Forming an interconnect layer (5) on at least one porous metal containing layer (1) of said second component;

At least two of the above in an optional order such as contacting the electrolyte layer 4 of the first component with the surface of the second component opposite the surface of the second component covered with the interconnect layer 5. Forming a stack of first and second components;

Sintering the stack; And

Injecting electrode material into the layers to form an anode and a cathode from the porous metal containing layer of the first and second components.

The present invention provides another method for producing a single stack of reversible solid oxide fuel cells, the method comprising the following steps:

Preparing at least one first component, characterized in that it comprises at least one porous metal containing layer (1), said at least one layer being an electrode layer;

Forming an electrolyte layer (4) on the electrode layer;

Sintering said first component under reducing conditions;

Forming at least one of a sealing layer and a spacer layer and an electrode layer on top of the electrolyte layer 4 of the first component, wherein the sealing layer is formed along the perimeter of the electrolyte layer on the electrolyte layer;

Preparing a second component, characterized in that it comprises at least one porous metal containing layer (1), said at least one layer being an electrode layer;

Forming an interconnect layer (5) on the porous metal containing layer;

Sintering said second component under reducing conditions;

Forming a sealing layer and / or a spacer layer and a contact layer on top of the interconnect layer (5) of the second component;

-Optionally forming a stack with at least two of said first and second components in order; And

Sealing / combining the stack.

The present invention provides a method for producing another single stack of reversible solid oxide fuel cells, the method comprising the following steps:

Preparing an elementary component comprising an electrolyte layer 11 and at least one porous metal containing layer 12, wherein at least one porous metal containing layer 12 is an electrode layer;

Forming the base component in a tube;

Forming a sealing layer on the ends of the base component;

Sintering the components in the form of a tube;

Welding an interconnector on the tube;

Injecting an electrode material into said metal layer to form an anode and / or cathode from said porous layer; And

Forming a stack with the components in the form of a tube.

The present invention finally provides a single stack of reversible solid oxide fuel cells that can be prepared according to the above methods.

Preferred embodiments are defined in the dependent claims.

In the following the invention will be explained in more detail.

First Concrete example

A first embodiment of the present invention relates to a method for producing a plate-shaped SOFC stack with external manifolding and to a SOFC monolithic stack that can be produced by the method.

The stack consists of two components. The first component comprises at least one metal containing layer 1. Preferably, the first component comprises at least two porous metal containing layers 1 and 2, more preferably the component comprises at least three porous metal containing layers 1, 2 and 3. The component is classified and has a porous structure. Such grading is a metal; Addition of mixed components such as electrolyte-metal, porosity, filler components, and tubes / fibers exhausted during the sintering process; And a plurality of layers that can vary with respect to layer thickness. The thicknesses of layers 1 and 2 range from about 20-70 μm, more preferably from about 30-40 μm. The thickness of layer 3 has a range of about 200-1000 μm, preferably about 300-700 μm, more preferably about 400-500 μm.

1 shows a first component comprising three porous metal containing layers 1, 2 and 3. Layer 1 has a minimum porosity. Electrolyte material is added to the layer with the minimum porosity to enhance bonding with the electrolyte. The component of FIG. 1 further comprises a layer 2 having a medium porosity below the electrode layer, which is continuous to the layer 3 having a high porosity.

The porosity of layer 1 is in the range of about 20-70%, preferably in the range of about 30-60%, more preferably in the range of about 40-50%. The average pore size is in the range of about 0.5-5 μm, preferably in the range of 0.5-3 μm, more preferably in the range of about 1-2 μm. If the first and / or second component comprises more than one metal containing layer, the porosity of layer 2 is in the range of about 30-70 μm, and the porosity of layer 3 is about 30- 80 μm range. Average pore sizes range from about 2-4 μm and about 3-10 μm, respectively. Porosity and pore size are measured by mercury intrusion (Hg-porosimetry).

All layers can be produced by tape casting. The slurry for casting the tape contains raw materials in powder form that may include binders, surfactants, solvents, various organic additives and other auxiliary ingredients. The components can be ball-milled together and then type cast into each of the layers using, for example, a doctor blade system. The layers are then stacked together to form a first component as shown in FIG. 2. Preferred additives for suspensions used for type casting include surfactants such as polyvinyl pyrrolidone (PVP), binders such as polyvinyl butyral (PVB) and solvents such as mixtures of ethanol and methylethylketone (EtOH + MEK) There is.

The raw materials used for the porous metal containing layer (1, 2, 3) is Ma is Ni, Ti, Ce, Mn, Mo, W, Co, La, Y or Al is Fe _{1 -x- y} Cr _x Ma _y alloys, Or NiO + metal oxides such as TiO ₂ or Cr ₂ O ₃ . The layers may also contain doped ceria or doped zirconia. Suitable dopants include Sc, Y, Ce, Ga, Sm, Gd, Ca and / or any Ln component or mixtures thereof. Preferred dopants for zirconia are Sc or Y. The preferred dopant for ceria is Gd. Ln is lanthanide.

The average granule size (d ₅₀ ) of the metal powder is generally in the range of about 3-25 μm, preferably in the range of about 7-15 μm. The average granule size of the oxide powder is in the range of about 0.05 to 5 μm, more preferably in the range of about 0.1-1 μm.

After lamination, the electrolyte layer 4 is spray sprayed on top of the first component. It may also be formed on the side of the first component, as shown in FIG. 2. In this case, when the first component includes two or more porous metal-containing layers 1 and 2 having different porosities, the layer having the smallest porosity among the two or more layers is an electrolyte layer ( 4) is formed on.

Preferably, a barrier layer 9 may be added before the electrolyte is injected on top. The barrier layer 9 may be formed from doped ceria. Suitable dopants are Sc, Y, Ce, Ga, Sm, Gd, Ca and / or any Ln component, or mixtures thereof. Preferably, the layer has a thickness in the range of about 0.1 to about 1 μm. The barrier layer 9 inhibits the interface action between the electrolyte and the electrode.

The second component comprises at least one porous metal containing layer (1), preferably at least two porous metal containing layers (1 and 2), more preferably at least three metal containing layers (1, 2 and 3). The layers of the second component correspond to the layers of the first component described above. An interconnect layer 5 is formed on top of the metal containing layer. If the second component comprises two or more porous metal containing layers (1, 2) having different porosities, the one having the highest porosity among the two or more layers is formed on the interconnect layer (5). . It can also be formed on the side of the interconnect layer as shown in FIG.

3 illustrates first and second components on which an electrolyte layer 4 and an interconnect layer 5 are formed, respectively.

An optional manufacturing process involves forming a high density foil, such as Fe 22 Cr foil, in the above mentioned layers. In this case, the high density foil is formed on the side of the layer 3 and the suspension is spray sprayed on the edge of the base component. Fe22Cr optionally contains a small amount of additives, and Fe, in balance with about 22% Cr by weight.

In addition, in some cases, it is desirable to add sintering accelerators / inhibitors to one or more of these layers to control and match the shrinkage profile during the sintering process.

The tape is then cut to a suitable length using, for example, a knife or a laser cutter. The first component and the second component, as shown in Figure 4, and the surface of the second component opposite the surface of the second component covered with the interconnect layer 5, the electrolyte layer of the first component; Form the stack in an optional manner such as to be in contact. If the first and second components are described above, if the top and sides of the component are covered with an electrolyte / interconnect layer then they are cut into suitable lengths, and only two opposite sides of the first and second components This is covered with the electrolyte / interconnect layer. In this case, the first and second components are rotated by 90 ° to form a stack, as shown in FIG. 5. Preferably, the stack is heat compressed.

The stack thus formed is sintered under reducing conditions at a desired temperature, such as in the range of about 900 ° C to about 1500 ° C. The sintering process for the plate-like structure includes a vertical load on the stack of 50-250 g / cm ² . The stack is heated with increasing air from about 20-50 ° C./h to about 500 ° C. After a dwell time of 1-10 hours, the furnace is emptied and H ₂ is introduced. After a stay time of 2-10 hours, the furnace is heated to a sintering temperature by increasing the temperature in the range of about 50-100 ° C./h and held for 1-10 hours before cooling to room temperature. In this case more than one sintering temperature may be applied. For example, two hours at 1100 ° C followed by four hours at 1250 ° C.

After sintering the stack, the electrodes are implanted. In the case of injecting the cathode, a cathode gas distribution channel is used. In this case, if the components comprise more than one layer, due to the classified porosity, the capillary phenomenon will migrate from the cathode material to the most dense layer, the cathode layer. Such injection is preferably done one or more times. It is also preferred that nitrate be used as starting material, in which case an intermediate heating process will be applied for the decomposition of the nitrate, which provides more space for the next injection process since the volume of the oxide is smaller than that of nitrate. .

Suitable materials for forming the cathode through the implantation process are LSM (La _{1 -x} Sr _x ) MnO _3-δ ), (Ln _{1 - x} Sr _x ) MnO _{3 -δ} , (Ln _{1 - x} Sr _x ) Fe _{1 - y} Co _y O _{3 -δ} , (Y _{1 - x} Ca _x ) Fe _{1 - y} Co _y O _{3 -δ} , (Gd _{1 -x} Sr _x ) Fe _1-y Co _y O _3-δ , (Gd _{1 - x Ca x) Fe 1} - y Co y O 3 -δ, (y, Ca) Fe 1 - y Co y O 3 -δ, doped ceria, and doped zirconia, or a material selected from the group consisting of a mixture thereof It includes. Ln is lanthanide.

In the above formula, δ is a number representing the deficiency of oxygen in the lattice, and depends on the composition and the actual partial pressure of oxygen (δ will increase as pO ₂ decreases). The number is generally between 0 and about 0.3.

As described for cathode injection, the anode is also injected accordingly. Suitable materials for forming the anode through the implantation process include materials selected from the group consisting of Ni, Ni-Fe alloys, doped ceria and doped zirconia or mixtures thereof. Dopants are the same as mentioned earlier. Alternatively Ma is Ba, Sr, Ca, Mb is V, Nb, Ta, Mo, W, Th, U, and Ma _s Ti _{1 - x} Mb _x O _{3 -δ with} 0 ≦ _s ≦ 0.5; Or M, T, V, Mn, Nb, Mo, W, Th, U can be used as the anode material LnCr _{1 - x} M _x O _{3 -δ} .

As described above, instead of tape casting each layer and laminating them successively, the first layer may be tape cast and then the dried further layer may be tape cast on top of the first layer. Optionally, each of the layers can be rolled out of a paste after laminating the layers. In another optional order, after lamination has been made, powder compaction can be applied to form each layer. It is preferred to hot press the sintered layer before sintering it.

The electrolyte / interconnect layers may be formed by spray injection as described above. Optionally, screen-printing; Electrophoretic deposition (EPD) followed by isostatic pressing; Alternatively, pulsed laser deposition (PLD) can be used.

Finally, an external manifold is formed on the side of the stack.

The single stack of reversible solid oxide fuel cells according to the invention is not only suitable for operating under atmospheric pressure but also can be used under increased pressure conditions, such as the specific pressure conditions of a gas turbine plant. For example, when a gas turbine is combined with the SOFC stack of the present invention, very high electrical efficiency of 60% or more can be achieved. Some heat generated by the SOFC stack can be used to generate electricity in the gas turbine to generate synergistic effects.

In addition, because of the complete monolithic structure, the SOFC stack of the present invention allows for differences in the lateral pressures of the anode and cathode, is easy to control, and makes plant construction simpler and less costly than conventional structures.

In particular, the interconnect layer and the porous substrate layer form the basis for providing excellent stability of a single structure.

Preferably, the SOFC stack can be used under increased pressure up to about 15 bar, more preferably 10 bar. Increased pressure in the present invention can be understood to be higher than atmospheric pressure at about 25 ℃.

Operation under increased pressure conditions has the advantage that the electromotive force (EMF) and rated power of the cell can be increased with increased pressure. In addition, an increase in pressure on the cathode side reduces cathode polarization loss and also leads to an increase in power, thus improving overall efficiency.

2nd Concrete example

A second embodiment of the present invention relates to a method for producing a plate-shaped structure SOFC stack with internal manifolding and to an SOFC stack produced by the method.

In this case, the at least one porous metal containing layer 1 of the first component of the second embodiment is identical to that described in the first embodiment. In the first process, the gas distribution holes are perforated on opposite sides as shown in FIG. 5. The diameter of the hole is generally in the range of about 5-7 mm, but can vary within the range of 1-10 mm. Thereafter, an electrolyte layer 4 is deposited on top of the metal containing layer having gas decomposition holes therein. Due to this, the perforated gas distribution holes and the four sides of the component are sealed as shown in FIG. 6.

Thus, the sealing layer 6 is deposited on the electrolyte layer 4, as shown in FIG. The sealing layer 6 is a thin layer with a preferred thickness of about 20 μm and comprises interconnect material (s) as described in the first embodiment above. This process can be performed by spray spraying or screen-printing. Alternatively, a sealing method based on ceramic and / or glass sealant that can be modified can be used.

Then, as shown in FIG. 8, holes are drilled in the two remaining sides of the first component. The initially formed gas distribution holes are sealed with the electrolyte layer 4, while these holes are left unsealed at the edges. Gas distribution to the electrode layer at the bottom of the electrolyte takes place through the unsealed hole.

The second component of the second embodiment is prepared as described above for the first component of the second embodiment in addition to the difference of applying the interconnect layer 5 instead of the electrolyte layer 4. The interconnect layer is formed on the portion with the highest porosity of the component. This is illustrated in Figures 10-13.

The first and second components are then preferably stacked and heat-compressed in an optional order with the second component rotated 90 ° as shown in FIG. 9. In Figure 9, the thickness of the layer is not shown to the exact relative size. Instead, the sealing layer is very thin as compared to the stack, so that the electrode layer of the interconnect component is in contact with the electrolyte from the electrolyte component in a wide area. Similarly, the current collector / gas distribution layer of the electrolyte component is brought into contact with the interconnect component.

Flow distribution for the cross flow design is shown in FIG. 15.

The process described above forms a cross flow structure. If a parallel flow or counter-flow configuration is desired, this can be done by perforating the gas distribution apertures arranged on the same opposite side. This is shown on FIGS. 16-19 for the first component. The second component is thus prepared. The advantage of parallel flow or opposite flow is that the cell does not have to be square.

After forming the stack, the four outer sides of the stack can be additionally sealed by applying a ceramic or glass layer.

The stack is then sintered. After sintering the electrodes are implanted as described in the first embodiment above.

The third Concrete example

In this embodiment, the anode and cathode are (partly) formed early in the process, thus reducing the need for an implantation process. Thus, the first component of the third embodiment contains an anode material in the electrode layer. The first component is sintered under reducing conditions after the sealing layer 6 and / or the contact layer 8 and the cathode layer are deposited. The cathode layer is preferably about 30 μm thick.

The second component of the third embodiment does not include an electrode layer. After sintering, the sealing layer 6 and the contact layer 8 are deposited.

The stack is formed by combining the first and second components in an optional order and seals / bonds them at low temperatures in the range of about 600 ° C. to about 900 ° C., preferably in the range of about 650 ° C. to about 850 ° C. Let's do it.

In a third embodiment, the need for electrode implantation is significantly reduced. However, the catalyst can be injected onto the anode and / or cathode if necessary. Suitable materials for injection are the same as listed in the first and second embodiments.

Fourth Concrete example

A fourth embodiment relates to a tubular structure SOFC stack and a method for manufacturing the same.

In this case, the method for producing the reversible solid oxide fuel cell stack includes the following steps:

Preparing a basic component comprising an electrolyte layer 11 and at least one metal containing layer 1 which is an electrode layer;

Forming a base component in the tube;

Forming a sealing layer at the end of the base component;

Sintering the components in the form of a tube on the tube;

Welding an interconnector on the tube;

Injecting a metal layer with electrode material to form an anode and / or cathode from the porous layers; And

Forming a stack with said tubular component.

The sintering is preferably performed at a temperature of about 900 ℃ to about 1500 ℃.

In addition, the manufacturing method includes a step of forming an electrode layer on the inner side of the tube-like component through the injection process after the sintering process. In addition, the outer side may be implanted to form an electrode layer.

In a preferred embodiment, the tubular component is prepared by rolling an uncut laminate comprising at least one electrolyte layer 11 and a porous metal-containing electrode layer 12 and sealing the tube at the junction. Can be. 22 illustrates a tube formed by lamination and rolling. The external electrode can be deposited on the tubular component after rolling and sealing. Optionally, external electrodes can be deposited on the laminate prior to rolling and sealing. 26 illustrates a stack structure.

According to the method of the present invention described in detail in connection with certain embodiments, a single stack is formed of basic components consisting of one or more metal containing layers having various porosities. The base components with electrolyte or interconnect layers are exhausted together to form a single stack; After this step, the electrodes are added through an implantation process.

Some embodiments have been described with reference to rectangular shapes, but the invention is not so limited. Depending on the preferred purpose of the stack, other forms may also be applied, for example circular.

In summary, the process of the invention described in the above preferred embodiments has numerous advantages:

1. The manufacturing method is simple; Sealed single stacks are made using only the sintering process;

2. The stack produced consists mostly of metal which can increase mechanical strength without including minimal glass sealing or glass sealing;

3. The stack may be provided 'ready to use' as a single component;

4. The interface action between the electrode and the electrolyte or between the interconnect and the electrode is impeded or limited by the injection method after the sintering process of the porous structure / stack. This allows the formation of electrodes with a large surface area and high performance;

5. The process is very flexible;

6. High metal content lowers the overall price of the stack;

7. The high metal content allows the current path through the stack to be through a metal with high conductivity. This can make nonplanar structures such as various tubular cells useful even with longer current paths;

8. The single stack of reversible solid oxide fuel cells produced can be used under pressurized conditions such as gas turbine plants. As such, a combined cycle plant can achieve high electrical efficiency, and the plant can also be simplified.

In the following, the invention will be explained with reference to the detailed examples. However, the present invention is not limited thereto.

1 shows a first component according to the invention with three metal containing layers 1, 2 and 3.

FIG. 2 shows a first half component according to the invention prior to forming the electrolyte / interconnect layers 4, 5. The arrow indicates the surface covered with the first component.

3 illustrates the first and second components according to the invention with the electrolyte / interconnect layers 4, 5 formed.

4 illustrates the structure of a stack according to the invention in which the first and second components are repeated.

5 illustrates the first component according to the invention after the internal gas distribution aperture for the cross flow design is formed.

6 illustrates the first component according to the invention comprising an internal gas distribution hole after the electrolyte layer 4 is formed for the cross flow structure.

7 illustrates a first component according to the invention comprising an internal gas distribution hole after the sealing layer 6 is formed on the first component for the cross flow structure.

8 illustrates the first component according to the invention after additional gas distribution holes have been formed for the cross flow structure.

9 illustrates the structure of a stack according to the invention in which the first and second components are repeated, including an internal gas distribution hole and a spacer / sealing layer 6 for a cross flow structure.

10 illustrates the second component according to the present invention after the internal gas distribution holes have been formed for the cross flow structure.

Figure 11 illustrates a second component according to the invention comprising an internal gas distribution hole after the interconnect layer 5 is formed on the second component for the cross flow structure.

Figure 12 illustrates a first embodiment according to the invention comprising an internal gas distribution hole after the sealing layer 6 is formed for the cross flow structure.

13 illustrates the first component according to the invention after additional gas distribution holes have been formed for the cross flow structure.

14 illustrates the structure of a stack according to the invention wherein the first and second components are repeated, including an internal gas distribution hole without a sealing layer for the cross flow structure.

15 illustrates a gas flow pattern for a cross flow structure in which an internal manifold is formed.

Figure 16 illustrates the first component according to the invention after the internal gas distribution holes for the co / counter flow design have been formed.

Figure 17 illustrates a first component according to the present invention comprising an internal gas distribution hole after the electrolyte layer is formed for the parallel / counter flow structure.

18 illustrates a first embodiment according to the invention comprising an internal gas distribution hole after the sealing layer 6 has been formed for parallel / opposite flow structures.

19 illustrates the first component according to the invention after additional gas distribution holes for the parallel / counterflow flow structure have been formed.

FIG. 20 illustrates the structure of a stack according to the present invention in which the first and second components are repeated, including an internal gas distribution hole and a spacer / sealing layer for the cross flow structure.

Figure 21 illustrates a basic component according to the invention comprising two porous metal containing layers 12, 13 and a high density electrolyte layer 11 free of one metal. Optionally, the base component may include a layer having a porous metal containing layer 14 formed on top of the electrolyte layer 11.

Figure 22 illustrates the wrapping of the base component around the tube prior to the sintering process.

23 illustrates filling the gap between the ends of the base component.

24 illustrates a cell after the sintering process (the cell is inserted into the tube during the sintering process).

25 illustrates a completed tubular cell after welding the interconnector.

FIG. 26 illustrates a finished cell including a cathode layer.

27 illustrates a stack formed of rolled tubular cells.

Example 1 Preparation of Single Stack with External Manifold

The first step involves tape-casting three metal containing layers (layers 1, 2 and 3, see FIG. 1). Suspensions for tape-casting are prepared by ball milling the powder with polyvinyl pyrrolidone (PVP), polyvinyl butyral (PVB) and EtOH + MEK as additives. After control of the particle size distribution, the suspension is tape-cast using a dual doctor blade system and the tapes are continuously dried.

Layer 1: 2 in volume ratio comprises: the suspension is a _-δ and Fe22Cr powder _{Zr 0 .78 Sc 0 .2 Y 0} .02 O 2 1. Green thickness is in the range of 50-70 μm. The porosity of the sintered layer has a pore size in the range of about 1-2 μm and represents about 50%.

Layer 2: The suspension is based on Fe22Cr using charcoal as pore former. The green thickness of the foil is in the range of 50-70 μm. The porosity of the sintered layer has an average pore size of about 4 μm and represents about 50%.

Layer 3: The same alloy composition used in Layer 2 was used, but in this case has a larger particle size distribution. Cellulose and graphite fibers were used as pore formers. The green thickness is about 500 μm. The porosity of the sintered layer has an average pore size of about 10 μm and represents about 60%.

The second step involves laminating the above-mentioned foils as the base component, as shown in FIG. This lamination step is carried out using a heated roll of a double roll set-up and consists of a single process.

The third step is to spray-cost, _-δ suspension _{Zr 0 .78 Sc 0 .2 Y 0} .02 O 2 on the (side of layer 1) and the edge surface of the base component, as shown in FIG. Steps. The suspension is prepared as described for the suspension in the first step.

The fourth step comprises spray painting the Fe22Cr suspension on the surface (side of layer 3) and the edge of the base component, as shown in FIG. The suspension is prepared as described for the suspension in the first step.

In the fifth step, the sprayed laminated tapes are cut into rectangular pieces. This is done by knife punching and forms a sintered portion in the range of 12 × 12 to 20 × 20 cm ² .

The sixth step includes forming a stack with two different components in an optional order, as shown in FIG.

In a seventh step, the stack is sintered. The stack is placed in a furnace under a vertical load of 150 g / cm ² . The stack is heated under flowing air by increasing it from about 50 ° C / h to about 500 ° C. After 2 hours of soaking, the furnace is emptied and H ₂ is introduced. After 3 hours of soaking, the furnace was heated to 100 ° C./h to heat to about 1250 ° C. and held for 5 hours before cooling to room temperature.

In the eighth step, the cathode is injected. The sintered stack is sealed two sides of the edge sealed with electrolyte by rubber sealing (see FIG. 4). Nitrate solutions of Gd, Sr, Co and Fe are vacuum infiltrated into the porous structure. The infiltration step is carried out four times with an intermediate heating step for the decomposition of nitrates. Is a composition made of the injected perovskite cathode (perovskite cathode) is _{(Gd 0 .6 Sr 0 .4)} 0.99 (Co 0 .2 Fe 0 .8) O 2 -δ.

In the ninth step, the anode is injected. The cathode-infused stack is sealed on two of the sides sealed with the interconnect by rubber sealing (see FIG. 4). Nitrates solutions of Ni, Ce and Gd are vacuum infiltrated into the porous structure. The infiltration step is carried out five times with an intermediate heating step in each infiltration step for the decomposition of nitrates. The prepared composition of the injected anode portion is 40% by volume Ni (after reducing NiO) and 60% by volume of (Ce _0.9 Gd _0.1 ) O _2-δ .

As such, a single stack prepared to be installed in an SOFC system was fabricated.

Example 2 Preparation of Single Stack (Thin Cell) with External Manifolding

The first step involves tape-casting three metal containing layers (layers 1, 2 and 3, see FIG. 1). Suspensions for tape-casting are prepared by ball milling powders with various organic additives such as surfactants, binders and solvents (see Example 1). After control of the particle size distribution, the suspension is tape-cast using a dual doctor blade system and the tapes are continuously dried.

Layer 1: 2 in volume ratio comprises: the suspension is a _-δ and Fe22Cr powder _{Zr 0 .78 Sc 0 .2 Y 0} .02 O 2 1. Green thickness is in the range of 30-40 μm. The porosity of the sintered layer has a pore size in the range of about 1-2 μm and represents about 40%.

Layer 2: The suspension is based on Fe22Cr using charcoal as a pore former. The green thickness of the foil is in the range of 30-40 μm. The porosity of the sintered layer has an average pore size of about 3 μm and represents about 40%.

Layer 3: The same alloy composition used in Layer 2 was used, but in this case has a larger particle size distribution. Cellulose and graphite fibers were used as pore formers. The green thickness is about 250 μm. The porosity of the sintered layer has an average pore size of about 8 μm and represents about 50%.

The second step includes laminating the foil prepared in the first step into the base component, as shown in FIG. This lamination step is carried out in one process using a heated roll.

Article as described in the step 3 shown in Figure 2, to the surface (layer 1 side of a) and on the edge _{Zr 0 .78 Sc 0 .2 Y 0} .02 O 2 -δ suspension of the base component spray painting A first basic ingredient (see FIG. 3) is prepared. The suspension is prepared as described for the suspension in the first step. 0.25 wt% Al ₂ O ₃ is added as a sintering agent.

In a fourth step, a second foundation component (see FIG. 3) is prepared by spray painting the Fe22Cr suspension onto the surface (side of layer 3) and the edge of the foundation component. The suspension is prepared as described for the suspension in the first step.

In the fifth step, the spray sprayed laminated tapes are cut into rectangular pieces. This is done by knife punching and pieces formed in the range of 12 × 12 to 20 × 20 cm ² after sintering are produced.

The sixth step forms a stack with the two different components prepared above in an optional order, as shown in FIG.

In a seventh step, the stack is sintered. The stack is placed in a furnace under a vertical load of 250 g / cm ² . The stack is heated under flowing air by increasing it from about 50 ° C / h to about 500 ° C. After 2 hours of soaking, the furnace is emptied and H ₂ is introduced. After a 3 hour soaking process, the furnace was heated to 100 ° C./h, heated to about 1150 ° C. and held for 8 hours before cooling to room temperature.

In the eighth step, the cathode is injected. The prepared sintered stack is sealed two sides of the edge sealed with electrolyte by rubber sealing (see FIG. 4). Nitrate solutions of Gd, Sr, Co and Fe are vacuum infiltrated into the porous structure. The infiltration step is carried out four times with an intermediate heating step for the decomposition of nitrates. A manufactured composition of the injected perovskite cathode is _{(Gd 0 .6 Sr 0 .4)} 0.99 (Co 0 .2 Fe 0 .8) O 2-δ.

In the ninth step, the anode is injected. The cathode injected stack is sealed with two of the sides sealed with a rubber seal (see FIG. 4). Nitrates solutions of Ni, Ce and Gd are vacuum infiltrated into the porous structure. The infiltration step is carried out five times with an intermediate heating step in each infiltration step for the decomposition of the injected nitrates. The prepared composition of the injected anode portion is 40% by volume Ni (after reducing NiO) and 60% by volume of (Ce _0.9 Gd _0.1 ) O _2-δ .

The fabricated stack is provided for installation in an SOFC system.

Example 3 Fabrication of a Single Stack with an External Manifold (Interconnect Foil)

The first step is performed as described in Embodiment 1.

The second step includes laminating the foil prepared in the first step into the base component, as shown in FIG. This lamination step is carried out in one process using a heated roll.

The third step is to stack the base components that receive the interconnect. A U-shaped high density Fe 22 Cr foil having a thickness of 50-100 μm was laminated together with the foil prepared in the first step. This component comprises four layers with a dense FeCr foil laminated to layer 3. In this process, as shown in Fig. 3, a second base component having a thicker interconnect layer than that shown in the figure is formed. This lamination is performed in one process using heated rolls.

The fourth step is identical to the third step of Example 1.

The fifth step includes cutting the laminated tape produced in the second step into pieces of squares of approximately the same size as described for the second basic component produced in the third step. This cutting step is performed by knife punching.

Subsequent manufacturing steps of the stack are performed as described in Steps 6-9 of Example 1.

The fabricated stack is provided for installation in an SOFC system.

Example 4a Fabrication of a Single Stack with Internal Manifolding and Cross Flow of Fuel and Oxidizing Gas.

The first step involves tape-casting three metal containing layers (layers 1, 2 and 3, see FIG. 1). Suspensions for tape-casting are prepared by ball milling powders with various organic additives such as surfactants, binders and solvents (see Example 1). After control of the particle size distribution, the suspension is tape-cast using a dual doctor blade system and the tapes are continuously dried.

Layer 1: 2 in volume ratio comprises: the suspension is a _-δ and Fe22Cr powder _{Zr 0 .78 Sc 0 .2 Y 0} .02 O 2 1. The green thickness is about 70 μm. The porosity of the sintered layer has a pore size in the range of about 1-2 μm and represents about 50%.

Layer 2: The suspension is based on Fe22Cr using charcoal as a pore former. The green thickness of the foil is about 100 μm. The porosity of the sintered layer has an average pore size of about 4 μm and represents 50-60%.

Layer 3: The same alloy composition used in Layer 2 was used, but in this case has a larger particle size distribution. Cellulose and graphite fibers were used as pore formers. The green thickness is about 400 μm. The porosity of the sintered layer has an average pore size of about 10-15 μm and represents about 70%.

The second step includes laminating the above-mentioned foils as the base component, as shown in FIG. This lamination step is carried out in one process using a heated roll.

In a third step, after cutting the foundation component into smaller pieces, holes (as shown in FIG. 5) are perforated on two opposite sides in the foundation component. This process can be carried out by knife punching or laser cutting. The diameter of the holes is about 5-7 mm and the size of the base component fragments range from 12 × 12 to 20 × 20 cm ² after sintering.

As the fourth step, shown in Figure 6 (the side of the layer 1), the surface of the base component and on the edge (edge of the outer edge and the _{hole) Zr 0 .78 Sc 0 .2 Y} 0 .02 O Spray painting the _{2 -δ} suspension to prepare a first basic component (see FIG. 3). The suspension is prepared as described for the suspension in the first step.

In the fifth step, as shown in FIG. 7, a sealing layer is formed near the edge. A layer having a thickness in the range of about 10-20 μm is prepared by screen painting Na-Al-SiO ₂ glass ink. The ink is prepared as described for the suspension in the first step.

In a sixth step, as shown in FIG. 8, the gas distribution holes are drilled on two opposite sides. This perforation step is performed as described above.

In the seventh step, as shown in Fig. 6, the Fe22Cr suspension is spray-painted onto the surface (side of layer 3) and the edge (outer edge and edge of the hole) of the base component to form a second base component (Fig. 3). Reference). The ink is prepared as described for the suspension in the first step.

In the eighth step, a sealing layer is formed at the edge portion. This part is shown in FIG. A layer having a thickness in the range of about 10-20 μm is prepared by screen painting Fe22Cr ink. The ink is prepared as described for the suspension in the first step.

In the ninth step, as shown in Fig. 8, the gas distribution holes on two opposite sides are drilled. The perforation step is performed as described above.

In a tenth step, as shown in FIG. 9, a stack is formed of the two different components in an optional order.

In the eleventh step the stack is sintered. The stack is placed in a furnace under a vertical load of 100 g / cm ² . The stack is then heated by increasing from about 50 ° C. to about 500 ° C. under flowing air. After 2 hours of soaking, the furnace is emptied and H ₂ is introduced. After 3 hours of soaking, the furnace is heated to about 100 ° C./h, heated to 1300 ° C. and held for 5 hours before cooling to room temperature.

In the twelfth step, the cathode is injected. The entrance of the anode portion is sealed with a rubber seal. Nitrate solutions of Gd, Sr, Co and Fe are vacuum infiltrated into the porous structure. The infiltration step is carried out four times with an intermediate heating step for the decomposition of nitrates. A manufactured composition of the injected perovskite cathode is _{(Gd 0 .6 Sr 0 .4)} 0.99 (Co 0 .2 Fe 0 .8) O 2-δ.

In the thirteenth step, an anode is injected. The entrance to the cathode portion is sealed with a rubber seal. Nitrates solutions of Ni, Ce and Gd are vacuum infiltrated into the porous structure. The infiltration step is carried out five times with an intermediate heating step in each infiltration step for the decomposition of the injected nitrates. The prepared compositions of the injected anode portion (after reduction of NiO) is 40% by volume of Ni and 60 _{vol% (Ce 0 .9 Gd 0 .1} ) O 2 -δ.

The fabricated stack is provided for installation in an SOFC system.

Example 4b Fabrication of a Single Stack with Internal Manifolding and Cross Flow of Fuel and Oxidizing Gas.

The stack was manufactured as described in Example 4a, but the fifth and eighth steps (sealing layer forming steps) were omitted as shown in FIG.

Example 4c Fabrication of a Single Stack with Internal Manifolding and Cross Flow of Fuel and Oxidizing Gas.

The stack was prepared as described in Examples 4a or 4b, but additionally included an outer seal formed on the side of the stack prior to the sintering process of the stack. The sealing is made by spray painting.

Example 5 Fabrication of a Single Stack with Internal Manifolding and Parallel or Opposite Flow of Fuel and Oxidizing Gas.

The first and second steps are performed as described in Example 3.

In the third step, not only the base component is cut into smaller pieces, but also the gas distribution holes are drilled on two opposite sides in the base component (as shown in FIG. 16). This process can be performed by knife punching or laser cutting. The diameter of the holes is generally about 5-7 mm and the size of the base component fragments range from 12 × 12 to 20 × 20 cm ² after sintering.

As the fourth step, shown in Figure 17, (on the side of the layer 1), the surface of the base component and on the edge (edge of the outer edge and the _{hole) Zr 0 .78 Sc 0 .2 Y} 0 .02 O Screen painting of the _{2 -δ} ink _produces a first basic component (see FIG. 3). The ink is prepared as described for the suspension in the first step.

In the fifth step, the sealing layer 6 is formed in the portion between the edge and the hole formed in the third step. A layer having a thickness in the range of about 10-20 μm is prepared by screen painting Ca—Al—SiO ₂ glass ink, as shown in FIG. 18. The ink is prepared as described for the suspension in the first step.

In the sixth step, a gas distribution hole is drilled between the holes formed in the third step. This perforation step is performed as described above.

In a seventh step, a second foundation component (see Fig. 3) is produced by screen painting Fe22Cr ink on the surface (side of layer 3) and on the edge (outer edge and edge of hole) of the foundation component. The ink is prepared as described for the suspension in the first step.

In the eighth step, a sealing layer is formed on the edge portion of the component prepared in the seventh step. A layer having a thickness in the range of 10-20 μm is prepared by screen painting Fe22Cr ink. The ink is prepared as described for the suspension in the first step.

In the ninth step, a gas distribution hole is drilled between the holes formed in the third step (see Fig. 19). This perforation step is performed as described above.

In a tenth step, as shown in FIG. 20, a stack is formed of the two different components in an optional order.

In the eleventh step, the stack is sintered. The stack is placed in a furnace under a vertical load of 50-250 g / cm ² . The stack is then heated by increasing from about 50 ° C. to about 500 ° C. under flowing air. After 2 hours of soaking, the furnace is cooled to room temperature and a metal titanium sponge is introduced into the front of the stack in the furnace, the furnace is emptied and H ₂ is introduced. The furnace is heated to about 100 ° C./h, heated to 1300 ° C. and held for 3 hours before cooling to room temperature.

In the twelfth step, the cathode is injected. The entrance of the anode portion is sealed by rubber sealing. 60 _{vol% (Gd 0 .6 Sr 0 .4} ) 0.99 (Co 0 .2 Fe 0 .8) O 2-δ and 40 _{vol% (Ce 0 .9 Gd 0 .1} ) O is a colloidal suspension of _{2 -δ} Vacuum infiltration into the porous structure. The infiltration step is carried out four times with an intermediate heating step.

In the thirteenth step, an anode is injected. The entrance to the cathode portion is sealed by a rubber seal. Nitrates solutions of Ni, Ce and Gd are vacuum infiltrated into the porous structure. The infiltration step is carried out five times with an intermediate heating step in each infiltration step for the decomposition of the injected nitrates. The prepared compositions of the injected anode portion (after reduction of NiO) is 45 vol% Ni and 55 _{vol% (Ce 0 .9 Gd 0 .1} ) O 2 -δ.

The fabricated stack is provided for installation in an SOFC system.

Example 6 Preparation of Single Stack with External Manifolding and Partial Injection of Electrodes

The first step is tape-casting four metal containing layers (layers 1, 2, 3 and 4). Suspensions for tape-casting are prepared by ball milling powders with various organic additives such as surfactants, binders and solvents. After control of the particle size distribution, the suspension is tape-cast using a dual doctor blade system and the tapes are continuously dried. The composition of the suspension can be adjusted to achieve the desired porosity as well as the sinter shrinkage.

Layer 1: The suspension comprises 55 wt% NiO and 45 _{wt% Zr 0 .78 Sc 0 .2 Y} 0 .02 O 2 -δ. Spherical PMMA is used as the pore former. The green thickness is about 50 μm. The porosity of the sintered layer has a pore size in the range of about 1-2 μm and represents about 50%.

Layer 2 includes in a volume ratio of 2: The suspension is a _-δ and Fe22Cr powder _{Zr 0 .78 Sc 0 .2 Y 0} .02 O 2 1. Charcoal was used as a pore former. The green thickness of the foil is 50-70 μm. The porosity of the sintered layer has a pore size in the range of about 4 μm and represents about 50%.

Layer 3: The suspension is based on Fe22Cr powder using charcoal as a pore former. The green thickness of the foil is about 50-70 μm. The porosity of the sintered layer has an average pore size of about 4 μm and represents 55%.

Layer 4: The same composition used in Layer 3 was used, but in this case has a larger particle size distribution. Cellulose and graphite fibers were used as pore formers. The green thickness is about 300 μm. The porosity of the sintered layer has an average pore size of about 10 μm and represents about 60%.

In the second step, the foil prepared in the first step is laminated to prepare a first basic component. The lamination step of these foils is performed in the order of layers 1, 2, 3 and 4 and using heated rolls.

Article as described in the step 3 shown in Figure 2, to the surface (layer 1 side of a) and on the edge _{Zr 0 .78 Sc 0 .2 Y 0} .02 O 2 -δ suspension of the base component spray painting An electrolyte is formed on the base component prepared in the second step. The suspension is prepared as described for the suspension in the first step.

The fourth step is to cut the sprayed laminated tape into rectangular pieces. This process is performed by knife punching and exhibits a fragment size in the range of 12 × 12 to 20 × 20 cm ² after sintering.

The fifth step is to sinter the first basic component prepared in the second to fourth steps. This sintering step is carried out as described in the seventh step of Example 1.

The sixth step is coating the sintered electrolyte on the first basic component together with the ceria barrier layer. The layer is formed by spin coating a nitrate solution of Ce and Gd. It is prepared compositions _{(Ce 0 .9 Gd 0 .1)} O 2 -δ.

The seventh step is to laminate the foils 2-4 prepared in the first step to prepare a second basic component. The laminating step of the foil is performed in the order of layers 2, 3 and 4 and using a roll to be heated.

The eighth step is spray painting Fe22Cr suspension on the surface (side of layer 4) and the edge of the base component to form an interconnect on the base component prepared in the sixth step, as shown in FIG. This is the step. The suspension is prepared as described for the suspension in the first step.

The ninth step is to cut the spray sprayed laminated tape into rectangular pieces. This is done by knife punching and exhibits a fragment size in the range of 12 × 12 to 20 × 20 cm ² after sintering.

The tenth step is the sintering of the second basic component prepared in the sixth to eighth steps. This sintering step is performed as described in the seventh step of Example 1.

The eleventh step is depositing Ca-Al-SiO ₂ based ink on the outer 5 mm of each side of the interconnect sealing side on the second base component.

The twelfth step is to form a cathode layer on the side of the layer 2 of the second basic component. _{(La 0 .6 Sr 0 .4)} 0.99 (Co 0 .2 Fe 0 .8) O 2-δ and (Ce _{0 0 .1 .9} Gd) ₂ O in 1 _-δ: 1 volume ratio of a mixture that contains the The cathode layer is formed by screen printing. This screen printing is performed as described above.

In the thirteenth step, the stack is formed of two different basic components in an optional order.

In the fourteenth step, the stack is heat-sealed at 850 ° C. for 2 hours in air to seal and bond the stack. The stack is subjected to a vertical load of 50 g / cm ² prior to this heat treatment.

The fifteenth step is injecting NiO to the anode portion by vacuum penetration of the Ni-nitrate solution.

The fabricated stack is provided for installation in an SOFC system.

Example 7 Fabrication of a Single Stack with External Manifolding and Partial Implantation of the Electrode

Example 7 is basically identical to Example 6 except that in the first step layer 1 is made of a mixture of nickel free anode material and Fe 22 Cr.

The fabricated stack is provided for installation in an SOFC system.

Example 8 Preparation of Tubular Cell Stacks

The first step is tape-casting the electrolyte layer and the two metal containing layers. Suspensions for tape-casting are prepared by ball milling powders with various organic additives such as surfactants, binders and solvents. After control of the particle size distribution, the suspension is tape-cast using a dual doctor blade system and the tapes are continuously dried. The composition of the suspension can be adjusted to achieve the desired porosity as well as the sinter shrinkage.

Layer 11: The suspension comprises _{Zr 0 .78 Sc 0 .2 Y 0} .02 O 2 -δ. Green thickness is in the range of 20-25 μm. The layer is sintered at a theoretical density of less than 96%.

Layer 12: 2 in volume ratio comprises: the suspension is a _-δ and Fe22Cr powder _{Zr 0 .78 Sc 0 .2 Y 0} .02 O 2 1. Green thickness ranges from 50-70 μm. The porosity of the sintered layer has a pore size in the range of about 1-2 μm and represents 50%.

Layer 13: The same composition used for layer 12 was used, but in this case has a larger particle size distribution. Cellulose and graphite fibers were used as pore formers. The green thickness is about 400 μm. The porosity of the sintered layer has an average pore size of about 10 μm and represents about 60%.

The second step is to laminate the foil prepared in the first step to prepare the base component. The lamination step of the foil is in the order of layers 11, 12 and 13, as shown in FIG. 21, and is performed using a heated roll.

The third step is to cut the base component into a sheet of size about 77 × 300 mm ² .

The fourth step is to wrap the base component around a yttria stabilized zirconia tube with an outer diameter of about 25 mm (see FIG. 22).

The fifth step is filling the gaps between the ends of the sheet with a paste comprising Fe 22 Cr powder (see FIG. 23).

The sixth step is to insert the wrapped tube into a larger support tube made of yttria stabilized zirconia (see FIG. 24).

The seventh step is a step of sintering under reducing conditions, as described in the seventh step of Example 1.

An eighth step is welding an interconnect rod to the tube, as shown in FIG. 25.

The ninth step is injecting an anode into the porous layer in the tube. This injection step is carried out by vacuum infiltration of Ni-, Ce- and Gd-nitrates, as described in the previous examples.

Step 10, as shown in Fig. _{26, (La 0 .6 Sr 0} .4) 0.99 (Co 0 .2 Fe 0 .8) O 2-δ and _{(Ce 0.9 Gd 0.1) O 2} -δ 1 A step of depositing a cathode by dip coating the tube in a slurry containing a volume ratio of 1: 1.

The eleventh step is to focus the single tube into a stack, as shown in FIG. 27.

The fabricated stack is provided for installation in an SOFC system.

Example 9 Preparation of Tubular Cell Stacks

The first step is identical to the first step of the seventh embodiment.

The second step is to laminate the foils prepared in the first step to produce the base component. The lamination step of the foil is carried out using rolls heated in the order of layers 14, 11, 12 and 13 (layer 14 may be similar to layer 12. As shown in FIG. The distance to the end of the component, after being wrapped shorter than the layer, is at least about 3 mm.

The third step is to cut the base component into sheets of size about 77 × 300 mm ² .

The fourth step is identical to the fourth to eighth steps of the eighth embodiment.

The ninth step is injecting an anode into the porous layer in the tube. The injection step is carried out by vacuum infiltration of Ni-, Ce- and Gd-nitrates, as described in the previous examples.

The tenth step is a step of injecting a porous layer to the outside of the tube. The tube is sealed at both ends, about 60 _{vol% (Gd 0 .6 Sr 0 .4} ) 0.99 (Co 0 .2 Fe 0 .8) O 2-δ and 40 _{vol% (Ce 0.9 Gd 0.1) O} 2 A colloidal suspension of _-δ is injected by dipping the tube into the suspension.

The eleventh step is to focus the single tube into a stack, as shown in FIG. 27.

The fabricated stack is provided for installation in an SOFC system.

It will be understood by those skilled in the art that various changes may be made in the form and details of the invention shown and described above. Such changes may be made within the scope of the following appended claims.

Claims (28)

1) a first component comprising at least one porous metal containing layer (1) having an electrolyte layer (4) combined with a sealing layer, wherein said at least one porous metal containing layer contains an electrode and said sealing layer is said electrolyte layer Formed along the perimeter of the electrolyte layer thereon; And 2) a second component comprising at least one porous metal containing layer (1) having an interconnect layer (5) combined with a sealing layer, wherein said at least one porous metal containing layer contains an electrode and said sealing layer is said interconnect layer Formed along the perimeter of the interconnect layer thereon; A first component and a second component, wherein at least one of the first component and the second component has two or more porous metal-containing layers (1), (2) having a classified porous structure The reversible solid oxide fuel cell (SOFC) single stack. delete delete Preparing a first component comprising at least one porous metal containing layer (1); Forming an electrolyte layer (4) on said at least one porous metal containing layer (1) of said first component; Preparing a second component comprising at least one porous metal containing layer (1); Forming an interconnect layer (5) on at least one porous metal containing layer (1) of said second component; Two or more in an optional order, such as contacting the electrolyte layer 4 of the first component with the surface of the second component opposite the surface of the second component covered with the interconnect layer 5. Forming a stack of the first and second components; Sintering the stack; And Injecting electrode material into the layers to form a cathode and an anode from the porous metal containing layer of the first and second components; Wherein at least one of the first component and the second component has a classified porous structure and comprises at least two porous metal containing layers (1) and (2). Method of making a stack. The method of claim 4, wherein the sintering step is performed at a temperature of 900 to 1500 ° C. 6. delete delete 6. The second component according to claim 4 or 5, opposite the at least one porous metal containing layer (1) of the first component and the interconnect layer (5) before the electrolyte layer (4) is formed. A method for producing a single stack of reversible solid oxide fuel cells, characterized in that a barrier layer (9) is formed on at least one of the at least one porous metal containing layer (1). delete 6. A layer according to claim 4 or 5, wherein the first component comprises at least two metal containing layers (1), (2) having different porosities, the least porosity of said at least two layers. The electrolyte layer (4) is formed in the manufacturing method of a single stack of reversible solid oxide fuel cell. 6. A layer according to claim 4 or 5, wherein the second component comprises at least two metal containing layers (1), (2) having different porosities, the second having at least one of the A method for producing a single stack of reversible solid oxide fuel cells, characterized in that an interconnect layer (5) is formed. 6. The method of claim 4 or 5, wherein the first component and the second component are perforated with two opposite sides before the electrolyte layer or the interconnect layer is formed so that a gas distribution hole is formed in the components. Method of manufacturing a single stack of reversible solid oxide fuel cells. The electrolyte layer or interconnect layer according to claim 12, wherein the sealing layer (6) is formed on the electrolyte layer or the interconnect layer after forming the electrolyte layer (4) or the interconnect layer (5) on the first component and the second component. A method of manufacturing a single stack of reversible solid oxide fuel cells, characterized in that it is formed along the perimeter of the deposited on the first and second components. 14. A reversible solid oxide fuel cell unit according to claim 13, wherein the two remaining sides of the first component and the second component are perforated after the sealing layer 6 is formed so that a gas distribution hole is formed in the components. Method of making a stack. 14. A method according to claim 13, wherein additional holes are perforated between gas distribution holes already perforated on the two opposite sides. 15. A method according to claim 14, wherein the sealing layer (6) comprises an electrode layer or a contact layer. Preparing at least one porous metal containing layer (1), said at least one layer being an electrode layer; Forming an electrolyte layer (4) on the electrode layer; Sintering said first component under reducing conditions; Forming at least one of a sealing layer and a spacer layer and an electrode layer on top of the electrolyte layer 4 of the first component, wherein the sealing layer is formed along the perimeter of the electrolyte layer on the electrolyte layer; Preparing a second component comprising at least one porous metal containing layer (1), said at least one layer being an electrode layer; Forming an interconnect layer (5) on the porous metal containing layer; Sintering said second component under reducing conditions; Forming at least one of a sealing layer and a spacer layer and a contact layer on top of the interconnect layer 5 of the second component, wherein the sealing layer is formed along the perimeter of the interconnect layer on the interconnect layer; -Optionally forming a stack with at least two of said first and second components in order; And Sealing / combining the stack; Wherein at least one of the first component and the second component has a classified porous structure and includes at least two porous metal containing layers (1) and (2). Method of preparation. 18. The method of claim 17, wherein the sintering step is performed at a temperature in the range of 900 ° C to 1500 ° C. 19. The method of claim 17 or 18, wherein the sealing / combining step is performed at a temperature in the range of 600 ° C to 900 ° C. 19. The method of claim 17 or 18, wherein said joining step is performed by soldering. Preparing an elementary component comprising an electrolyte layer (11) and at least one porous metal containing layer (12), said at least one porous metal containing layer (12) being an electrode layer; Forming the base component in a tube; Forming a sealing layer at the end of the base component; Sintering the components in the form of a tube; Welding an interconnector to the tube; Injecting a metal layer with electrode material to form at least one of an anode and a cathode from the porous layer; And Forming a stack of said tubular components; The method of claim 1, wherein the basic component has two or more porous metal-containing layers (1) and (2) while having a classified porous structure. 22. The method of claim 21, further comprising forming an electrode layer on the inner side of the tubular component by implantation after the sintering step. 23. The method of claim 21 or 22, further comprising forming an electrode layer on the outer side of the tubular component by implantation after the sintering step. 23. The method of claim 21 or 22, wherein the sintering step is performed at a temperature in the range of 900 ° C to 1500 ° C. 22. The method of claim 21, wherein an external electrode layer is deposited on the tubular component after welding the current collector. A reversible solid oxide fuel cell stack prepared according to the method of claim 4 or 5. A method of using the reversible solid oxide fuel cell stack according to claim 1 under increased pressure conditions up to 15 bar. A method of using the reversible solid oxide fuel cell stack according to claim 1 for generating electricity with a turbine.

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